US4123517A - Toothpaste compositions - Google Patents
Toothpaste compositions Download PDFInfo
- Publication number
- US4123517A US4123517A US05/645,743 US64574375A US4123517A US 4123517 A US4123517 A US 4123517A US 64574375 A US64574375 A US 64574375A US 4123517 A US4123517 A US 4123517A
- Authority
- US
- United States
- Prior art keywords
- toothpaste
- weight
- phosphate ester
- anionic phosphate
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000606 toothpaste Substances 0.000 title claims abstract description 48
- 229940034610 toothpaste Drugs 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 17
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 16
- 239000010452 phosphate Substances 0.000 claims abstract description 16
- 238000005498 polishing Methods 0.000 claims abstract description 10
- 150000005690 diesters Chemical class 0.000 claims abstract description 5
- -1 anionic phosphate ester Chemical class 0.000 claims description 35
- 239000004411 aluminium Substances 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- KZNNRLXBDAAMDZ-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane trihydrate Chemical compound O.O.O.O=[Al]O[Al]=O KZNNRLXBDAAMDZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 9
- 125000000129 anionic group Chemical group 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- ZBJVLWIYKOAYQH-UHFFFAOYSA-N naphthalen-2-yl 2-hydroxybenzoate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=C(C=CC=C2)C2=C1 ZBJVLWIYKOAYQH-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000000551 dentifrice Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000003981 vehicle Substances 0.000 description 5
- XGRSAFKZAGGXJV-UHFFFAOYSA-N 3-azaniumyl-3-cyclohexylpropanoate Chemical compound OC(=O)CC(N)C1CCCCC1 XGRSAFKZAGGXJV-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000796 flavoring agent Substances 0.000 description 4
- 239000003349 gelling agent Substances 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 229960004711 sodium monofluorophosphate Drugs 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- 235000003599 food sweetener Nutrition 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000003906 humectant Substances 0.000 description 3
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 235000013772 propylene glycol Nutrition 0.000 description 3
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- 239000003765 sweetening agent Substances 0.000 description 3
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 description 3
- 150000004684 trihydrates Chemical class 0.000 description 3
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- BACYUWVYYTXETD-UHFFFAOYSA-N N-Lauroylsarcosine Chemical compound CCCCCCCCCCCC(=O)N(C)CC(O)=O BACYUWVYYTXETD-UHFFFAOYSA-N 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920001983 poloxamer Polymers 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 108700004121 sarkosyl Proteins 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- ZFTPXVSCHFZJNO-UHFFFAOYSA-N (1e)-1-[amino-(4-chloroanilino)methylidene]-2-dodecylguanidine Chemical compound CCCCCCCCCCCCN=C(N)N=C(N)NC1=CC=C(Cl)C=C1 ZFTPXVSCHFZJNO-UHFFFAOYSA-N 0.000 description 1
- OQYNFBPKTVQOKO-UHFFFAOYSA-N 1,1-dichlorooctane Chemical compound CCCCCCCC(Cl)Cl OQYNFBPKTVQOKO-UHFFFAOYSA-N 0.000 description 1
- DTOUUUZOYKYHEP-UHFFFAOYSA-N 1,3-bis(2-ethylhexyl)-5-methyl-1,3-diazinan-5-amine Chemical compound CCCCC(CC)CN1CN(CC(CC)CCCC)CC(C)(N)C1 DTOUUUZOYKYHEP-UHFFFAOYSA-N 0.000 description 1
- PBYSGNVIJLMHLI-UHFFFAOYSA-N 1-[n'-[(4-chlorophenyl)methyl]carbamimidoyl]-2-(3-dodecoxypropyl)guanidine Chemical compound CCCCCCCCCCCCOCCCNC(=N)NC(=N)NCC1=CC=C(Cl)C=C1 PBYSGNVIJLMHLI-UHFFFAOYSA-N 0.000 description 1
- GNRHJCJPGSPGHI-UHFFFAOYSA-N 1-[n'-[(4-chlorophenyl)methyl]carbamimidoyl]-2-[(2,4-dichlorophenyl)methyl]guanidine Chemical compound C1=CC(Cl)=CC=C1CNC(=N)NC(=N)NCC1=CC=C(Cl)C=C1Cl GNRHJCJPGSPGHI-UHFFFAOYSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- HTYFFCPFVMJTKM-UHFFFAOYSA-N 2-(4-chlorophenyl)-1-(diaminomethylidene)guanidine Chemical compound NC(N)=NC(N)=NC1=CC=C(Cl)C=C1 HTYFFCPFVMJTKM-UHFFFAOYSA-N 0.000 description 1
- XEBPUCFKEPJQFT-UHFFFAOYSA-N 2-(5,6-dichloro-1h-benzimidazol-2-yl)guanidine Chemical compound ClC1=C(Cl)C=C2NC(N=C(N)N)=NC2=C1 XEBPUCFKEPJQFT-UHFFFAOYSA-N 0.000 description 1
- LFJJOPDNPVFCNZ-UHFFFAOYSA-N 2-[hexadecanoyl(methyl)amino]acetic acid Chemical class CCCCCCCCCCCCCCCC(=O)N(C)CC(O)=O LFJJOPDNPVFCNZ-UHFFFAOYSA-N 0.000 description 1
- NGOZDSMNMIRDFP-UHFFFAOYSA-N 2-[methyl(tetradecanoyl)amino]acetic acid Chemical class CCCCCCCCCCCCCC(=O)N(C)CC(O)=O NGOZDSMNMIRDFP-UHFFFAOYSA-N 0.000 description 1
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical compound CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 description 1
- UBLAMKHIFZBBSS-UHFFFAOYSA-N 3-Methylbutyl pentanoate Chemical compound CCCCC(=O)OCCC(C)C UBLAMKHIFZBBSS-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000416162 Astragalus gummifer Species 0.000 description 1
- 238000004131 Bayer process Methods 0.000 description 1
- 229940123208 Biguanide Drugs 0.000 description 1
- GHXZTYHSJHQHIJ-UHFFFAOYSA-N Chlorhexidine Chemical compound C=1C=C(Cl)C=CC=1NC(N)=NC(N)=NCCCCCCN=C(N)N=C(N)NC1=CC=C(Cl)C=C1 GHXZTYHSJHQHIJ-UHFFFAOYSA-N 0.000 description 1
- 241000206575 Chondrus crispus Species 0.000 description 1
- 244000223760 Cinnamomum zeylanicum Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 229910021593 Copper(I) fluoride Inorganic materials 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- UDIPTWFVPPPURJ-UHFFFAOYSA-M Cyclamate Chemical compound [Na+].[O-]S(=O)(=O)NC1CCCCC1 UDIPTWFVPPPURJ-UHFFFAOYSA-M 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 235000019739 Dicalciumphosphate Nutrition 0.000 description 1
- 239000004150 EU approved colour Substances 0.000 description 1
- 244000004281 Eucalyptus maculata Species 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 240000001238 Gaultheria procumbens Species 0.000 description 1
- 235000007297 Gaultheria procumbens Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 244000024873 Mentha crispa Species 0.000 description 1
- 235000014749 Mentha crispa Nutrition 0.000 description 1
- 244000246386 Mentha pulegium Species 0.000 description 1
- 235000016257 Mentha pulegium Nutrition 0.000 description 1
- 235000004357 Mentha x piperita Nutrition 0.000 description 1
- 244000227633 Ocotea pretiosa Species 0.000 description 1
- 235000004263 Ocotea pretiosa Nutrition 0.000 description 1
- 235000011203 Origanum Nutrition 0.000 description 1
- 240000000783 Origanum majorana Species 0.000 description 1
- 238000013494 PH determination Methods 0.000 description 1
- XCOJIVIDDFTHGB-UEUZTHOGSA-N Perillartine Chemical compound CC(=C)[C@H]1CCC(\C=N\O)=CC1 XCOJIVIDDFTHGB-UEUZTHOGSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 235000016639 Syzygium aromaticum Nutrition 0.000 description 1
- 244000223014 Syzygium aromaticum Species 0.000 description 1
- 229920001615 Tragacanth Polymers 0.000 description 1
- DXEDAFCGZSAFIA-UHFFFAOYSA-N [N'-[(4-chlorophenyl)-phenylmethyl]carbamimidoyl]urea Chemical compound C=1C=C(Cl)C=CC=1C(NC(=N)NC(=O)N)C1=CC=CC=C1 DXEDAFCGZSAFIA-UHFFFAOYSA-N 0.000 description 1
- HFIGWKOFZLNOQK-UHFFFAOYSA-K [O-]P([O-])(=O)OP(=O)([O-])O.[Ca+2].[Na+] Chemical class [O-]P([O-])(=O)OP(=O)([O-])O.[Ca+2].[Na+] HFIGWKOFZLNOQK-UHFFFAOYSA-K 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229960003260 chlorhexidine Drugs 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical class C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 235000017803 cinnamon Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 239000000625 cyclamic acid and its Na and Ca salt Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 description 1
- 229910000390 dicalcium phosphate Inorganic materials 0.000 description 1
- 229940038472 dicalcium phosphate Drugs 0.000 description 1
- DGTVXEHQMSJRPE-UHFFFAOYSA-N difluorophosphinic acid Chemical compound OP(F)(F)=O DGTVXEHQMSJRPE-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 229940091249 fluoride supplement Drugs 0.000 description 1
- OMRRUNXAWXNVFW-UHFFFAOYSA-N fluoridochlorine Chemical compound ClF OMRRUNXAWXNVFW-UHFFFAOYSA-N 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 229910001385 heavy metal Chemical class 0.000 description 1
- SNKKBYWIYDOXGC-IYEMJOQQSA-N hexane;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanoic acid Chemical compound CCCCCC.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O SNKKBYWIYDOXGC-IYEMJOQQSA-N 0.000 description 1
- 235000001050 hortel pimenta Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 229910000400 magnesium phosphate tribasic Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229960001047 methyl salicylate Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000000214 mouth Anatomy 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- ZMRUPTIKESYGQW-UHFFFAOYSA-N propranolol hydrochloride Chemical compound [H+].[Cl-].C1=CC=C2C(OCC(O)CNC(C)C)=CC=CC2=C1 ZMRUPTIKESYGQW-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 235000002020 sage Nutrition 0.000 description 1
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical class C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229960001462 sodium cyclamate Drugs 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- KSAVQLQVUXSOCR-UHFFFAOYSA-M sodium lauroyl sarcosinate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CC([O-])=O KSAVQLQVUXSOCR-UHFFFAOYSA-M 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 1
- 229960002799 stannous fluoride Drugs 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/26—Aluminium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/55—Phosphorus compounds
- A61K8/556—Derivatives containing from 2 to 10 oxyalkylene groups
Definitions
- This invention relates to a toothpaste composition.
- a toothpaste composition which is compatible with an unlined aluminium container such as a toothpaste tube.
- Hydrated alumina such as alpha alumina trihydrate (e.g. Gibbsite) is a desirable polishing agent for dental surfaces and has been incorporated into toothpaste compositions.
- the alkalinity of hydrated alumina is such that when a toothpaste containing it is incorporated into an unlined aluminium container such as a toothpaste tube, gas formation, causing container swelling, often occurs as does etching of the aluminium surface.
- a toothpaste composition which contains hydrated alumina as polishing agent and a particular anionic foaming surface active agent which permits the use of the toothpaste composition in an unlined aluminium container without undue incompatibility.
- this invention relates to a toothpaste composition
- a toothpaste composition comprising a dentally acceptable oral vehicle and dispersed therein about 20 - 75% by weight of a polishing material including hydrate of alumina in amount of at least 10% by weight of the toothpaste, and about 0.05 - 5% by weight of an anionic phosphate ester surface active agent comprising a mixture of monoester of the formula ##STR1## and DIESTER OF THE FORMULA ##STR2## wherein R is an alkyl group of 10-20 carbon atoms, n is an integer from 1-6 and M is selected from the group consisting of hydrogen, alkali metal and ammonium, said toothpaste having a pH of up to about 9.5.
- this invention relates to a packaged toothpaste composition
- a packaged toothpaste composition comprising an unlined aluminium container and contained therein in contact with the aluminium surface of said container the above described toothpaste composition.
- the hydrated alumina employed is an alpha alumina trihydrate.
- a conventional way of manufacturing this material is by the Bayer process. In that process the alpha alumina trihydrate is precipitated from a solution of sodium aluminate. See Encyclopedia of Chemical Technology, Kirk-Othmer, 2nd. Edition, Vol. 1, pages 937-941, and Vol. 2, pages 41-45 and 50-51.
- the trihydrate compound is precipitated in the form of granules or agglomerates which are too large for general use as a dentifrice polishing material, e.g. about 40 to 100 microns diameter. Therefore the granules or agglomerates, after drying (sometimes after water-washing and drying) are ground to a suitable particle size, e.g. to an average particle diameter in the range of about 2 to 20 microns, such as about 5 to 10 microns in diameter.
- the washed unground granules usually show an alkaline reaction when slurried in water.
- the pH of a 10% or 20% by weight of trihydrate slurry at room temperature may be in the range of about 7.5, 8.5, 9 or 9.5.
- the pH can be measured with an Orion model 801 Digital pH/mv meter which is fitted with an EIL model 1150 combination pH and reference electrode.
- the instrument is first calibrated at room temperature by placing the electrode into 50 ml of pH 7 buffer solution in a 100 ml beaker, and adjusting the calibration control until the instrument reading corresponds to a buffer pH.
- the electrode is then removed, washed with deionized water, and placed into 125 gms of a pre-prepared 20% slurry of the trihydrate sample in deionized water, in a 250 ml beaker, and its pH reading taken.
- the anionic phosphate esters are mixtures of mono and di-esters of the formulas hereinabove set forth. They are available from MoDo Kemi Aktiebolaget, formerly Berol Aktiebolaget, of Sweden, under the name Berol and may include an anionic tri-ester moiety too, as well as some non-ionic portion. They may be used in acid or partially or fully neutralised forms. Berol 729 has alkyl chain lengths of 16-18 carbon atoms and contains series of 4 ethylene oxide units.
- Berol 525 which contains alkyl groups of 10-18 carbon atoms and series of 5 ethylene oxide units
- Berol 513 which contains alkyl groups of 16-18 carbon atoms.
- Berol anionic phosphate esters are available as Berol 521, Berol 724 and Berol 733.
- the weight ratio of mono-ester to di-ester may vary, typically from about 1:10 to 10:1.
- the acid forms of the anionic phosphate ester surface active agents are neutralised or partially neutralised, alkali metal, preferably sodium, or ammonium cations are present.
- the surface active agent is employed in the oral preparation in amount of about 0.05-5% by weight, preferably about 0.5- 3% and most preferably about 0.5-2%.
- the phosphate esters serve to improve dentifrice consistency and body.
- the toothpaste may comprise an additional dentally acceptable water-insoluble polishing material, such as calcined alumina, dehydrated silica, crystalline silica, having particles of sizes up to about 5 microns, a mean particle size of up to 1.1 microns and a surface area of up to 50,000 cm 2 /gm, water-insoluble sodium metaphosphate (preferably substantially free of water-solubles content), tricalcium phosphate, dihydrated dicalcium phosphate, anhydrous dicalcium phosphate, calcium pyrophosphate, magnesium orthophosphate, trimagnesium phosphate, calcium carbonate, aluminium silicate, zirconium silicate, bentonite and mixtures thereof. At least 10% of the toothpaste is hydrated alumina.
- an additional dentally acceptable water-insoluble polishing material such as calcined alumina, dehydrated silica, crystalline silica, having particles of sizes up to about 5 microns, a mean particle size of up to 1.1 microns and a surface area of up to
- the polishing material is generally present in amounts of about 20-75% by weight of a toothpaste containing it, about 30-55% being preferable.
- Preferably about 20-55% of the toothpaste is hydrated alumina.
- the liquid vehicle may comprise water, typically in amount of about 10-90% by weight of the preparation.
- the liquid vehicle may additionally or alternatively comprise humectants such as glycerine, sorbitol solution propylene glycol.
- humectants such as glycerine, sorbitol solution propylene glycol.
- a mixture of water and glycerine and/or sorbitol solution is particularly advantageous.
- Preferably about 20-40% by weight of humectant and 10 to about 45% by weight of water is present.
- the solid portion of the vehicle of a paste or gel composition is a gelling agent or binder such as hydroxyethyl cellulose and hydroxypropyl cellulose. These gelling agents are particularly preferred since they do not provide ions to the composition. Other gelling agents which may be used include Irish moss, gum tragacanth, sodium carboxymethyl cellulose, polyvinyl pyrrolidone, starch and water-soluble hydrophilic colloidal carboxyvinyl polymers such as those sold under the name Carbopol 934 and 940.
- the toothpaste is placed in an extrudable tube of unlined aluminium for easy application to a toothbrush.
- the toothpastes may include an organic surface active agent in addition to the anionic phosphate ester surface active agent.
- additional agent may be anionic, nonionic, cationic or ampholytic in nature, and it is preferred to employ as the surface-active agent a detersive material which imparts to the dentifrice detersive and foaming properties.
- Suitable types of such detergents are water-soluble salts of higher (i.e.
- fatty acid monoglyceride monosulphates such as the sodium salt of the monosulphated monoglyceride of hydrogenated coconut oil fatty acids, high alkyl sulphates, such as sodium lauryl sulphate, alkyl aryl sulphonates, such as sodium dodecyl benzene sulphonate, olefin sulphonates, such as sodium olefin sulphonate in which the olefin group contains 12- 21 carbon atoms, higher alkyl sulphoacetates, higher fatty acid esters of 1,2-dihydroxy propane sulphonates, and the substantially saturated higher aliphatic acyl amides of lower (i.e.
- aliphatic amino carboxylic acid compounds such as those having 12- 16 carbons in the fatty acid, alkyl or acyl radicals.
- amides are N-lauroyl sarcosine, and the sodium, potassium and ethanolamine salts of N-lauroyl, N-myristoyl or N-palmitoyl sarcosine, which should be substantially free from soap or similar higher fatty acid material which tends to substantially reduce the effect of these compounds.
- the use of these sarcosine compounds in dentifrices is particularly advantageous since these materials exhibit a prolonged and marked effect in the inhibition of acid formation in the oral cavity due to carbohydrates breakdown in addition to exerting some reduction in the solubility of tooth enamel in acid solutions.
- Nonionic agents such as condensates of sorbitan monostearate with approximately 60 moles of ethylene oxide, condensates of ethylene oxide with propylene oxide condensates of propylene glycol ("Pluronics"-PLURONIC is a Trade Mark) and amphoteric agents such as quaternised imidazole derivatives, which are availabe under the trade name "Miranol” such as Miranol C2M.
- Cationic surface active germicides and antibacterial compounds such as diisobutylphenoxyethoxyethyl dimethyl benzyl ammonium chloride, benzyl dimethyl stearyl ammonium chloride, tertiary amines having one fatty alkyl group (of from 12- 18 carbon atoms) and two (poly) oxyethylene groups attached to the nitrogen (typically containing a total of from 20 to 50 ethanoxy groups per molecule) and salts thereof with acids, and compounds of the structure ##STR3## wherein R is a fatty alkyl group typically containing from 12 to 18 carbon atoms, and x, y and z total 3 or higher, as well as salts thereof with mineral or organic acids, may also be used. It is preferred that the total amount of surface active agent not exceed about 5% by weight of the oral composition. At least about 0.05% of the oral composition should be composed of the anionic phosphate ester surface active agent.
- a fluorine-providing compound is present in the oral preparation.
- These compounds may be slightly soluble in water or may be fully water-soluble. They are characterised by their ability to release fluoride ions in water and by substantial freedom from reaction with other compounds of the oral preparation.
- inorganic fluoride salts such as suitable alkali metal, alkaline earth metal, and heavy metal salts, for example, sodium fluoride, potassium fluoride, ammonium fluoride, a copper fluoride such as cuprous fluoride, zinc fluoride, a tin fluoride such as stannic fluoride, or stannous chlorofluoride, barium fluoride, sodium fluorosilicate, ammonium fluorosilicate, sodium fluoro-zirconate, sodium monofluorophosphate, aluminium mono- and di-fluorophosphate, and fluorinated sodium calcium pyrophosphate.
- Alkali metal and tin fluorides such as sodium and stannous fluorides and particularly sodium monofluorophosphate are preferred.
- the amount of the fluorine-providing compound is dependent to some extent upon the type of compound, its solubility, and the type of oral preparation, but it must be a non-toxic amount. It is considered that an amount of such compound which releases a maximum of 1% by weight, based on the weight of the preparation, is satisfactory. Any suitable minimum amount of such compound may be used, but it is preferable to employ sufficient compound to release from 0.005% to 1%, most preferably about 0.1%, by weight of fluoride ion. Typically, in the cases of alkali metal fluoride and stannous fluoride, this component is present in an amount up to 2% by weight, based on the weight of the preparation, and preferably in the range of from 0.05% to 1%. In the case of sodium monofluorophosphate the compound may be present in an amount up to 7.6% by weight, more typically 0.76%.
- Antibacterial agents may also be present, typically in an amount of 0.01- 5% by weight.
- Typical antibacterial agents include
- flavouring or sweetening materials may also be employed.
- suitable flavouring constituents are flavouring oils, e.g. oils of spearmint, peppermint, wintergreen, sassafras, clove, sage, eucalyptus, marjoram, cinnamon, lemon and orange, and methylsalicylate.
- suitable sweetening agents include sucrose, lactose, maltose, sorbitol, sodium cyclamate, perillartine, and saccharin.
- flavour and sweetening agent may together comprise from 0.01% to 5% or more of the preparation.
- the toothpaste typically has a pH of about 4 - 10, preferably about 5 - 9.
- a pH of about 4 - 10, preferably about 5 - 9.
- the toothpastes are typically prepared by dispersing polishing material in the dental vehicle and adding the phosphate ester and other components thereto.
- the following toothpastes are prepared by mixing gelling agent and sweetener with humectant, thereafter adding polishing agent, whitener, water and surface-active agent, and finally flavour.
- the toothpastes are deaerated and placed in unlined aluminium tubes.
- the toothpastes remain satisfactorily compatible with the unlined aluminium tubes which contain them upon storage for 6 months at room temperature, at accelerated aging conditions of 43° C. for 3 months.
- tube compatibility occurs when the above toothpaste formulation containing the various phosphate esters includes 4.723 parts of 1,6-di-(p-chlorophenyl biguanido)hexane digluconate (20% soln) in one set of cases or 0.76 parts of sodium monofluorophosphate in another set of cases, with the formula amount of water being correspondingly reduced.
- the toothpaste remains compatible with the aluminium tube upon accelerated aging for 3 months at 43° C. as well as upon aging at room temperature for 3 months.
Abstract
Toothpaste composition having desirable compatibility with an unlimited aluminum container, which toothpaste contains a polishing material comprising hydrate of alumina and an anionic phosphate mono- or di-ester.
Description
This invention relates to a toothpaste composition. In particular it relates to a toothpaste composition which is compatible with an unlined aluminium container such as a toothpaste tube.
Hydrated alumina such as alpha alumina trihydrate (e.g. Gibbsite) is a desirable polishing agent for dental surfaces and has been incorporated into toothpaste compositions. The alkalinity of hydrated alumina is such that when a toothpaste containing it is incorporated into an unlined aluminium container such as a toothpaste tube, gas formation, causing container swelling, often occurs as does etching of the aluminium surface.
It is an advantage of this invention that a toothpaste composition is provided which contains hydrated alumina as polishing agent and a particular anionic foaming surface active agent which permits the use of the toothpaste composition in an unlined aluminium container without undue incompatibility.
In accordance with certain of its aspects this invention relates to a toothpaste composition comprising a dentally acceptable oral vehicle and dispersed therein about 20 - 75% by weight of a polishing material including hydrate of alumina in amount of at least 10% by weight of the toothpaste, and about 0.05 - 5% by weight of an anionic phosphate ester surface active agent comprising a mixture of monoester of the formula ##STR1## and DIESTER OF THE FORMULA ##STR2## wherein R is an alkyl group of 10-20 carbon atoms, n is an integer from 1-6 and M is selected from the group consisting of hydrogen, alkali metal and ammonium, said toothpaste having a pH of up to about 9.5.
In accordance with certain of its additional aspects, this invention relates to a packaged toothpaste composition comprising an unlined aluminium container and contained therein in contact with the aluminium surface of said container the above described toothpaste composition.
The hydrated alumina employed is an alpha alumina trihydrate. A conventional way of manufacturing this material is by the Bayer process. In that process the alpha alumina trihydrate is precipitated from a solution of sodium aluminate. See Encyclopedia of Chemical Technology, Kirk-Othmer, 2nd. Edition, Vol. 1, pages 937-941, and Vol. 2, pages 41-45 and 50-51. The trihydrate compound is precipitated in the form of granules or agglomerates which are too large for general use as a dentifrice polishing material, e.g. about 40 to 100 microns diameter. Therefore the granules or agglomerates, after drying (sometimes after water-washing and drying) are ground to a suitable particle size, e.g. to an average particle diameter in the range of about 2 to 20 microns, such as about 5 to 10 microns in diameter.
The washed unground granules usually show an alkaline reaction when slurried in water. For instance, depending on the degree of washing before drying, the pH of a 10% or 20% by weight of trihydrate slurry at room temperature may be in the range of about 7.5, 8.5, 9 or 9.5.
The pH can be measured with an Orion model 801 Digital pH/mv meter which is fitted with an EIL model 1150 combination pH and reference electrode. The instrument is first calibrated at room temperature by placing the electrode into 50 ml of pH 7 buffer solution in a 100 ml beaker, and adjusting the calibration control until the instrument reading corresponds to a buffer pH. The electrode is then removed, washed with deionized water, and placed into 125 gms of a pre-prepared 20% slurry of the trihydrate sample in deionized water, in a 250 ml beaker, and its pH reading taken.
On grinding the alkalinity thus measured increases and the pH (measured as above) of the ground, unwashed material is generally above about 8. For instance the pH on grinding may change as follows: 7.5 (before grinding) to 8.8 (after grinding); 8.8 (before) to 9.2 (after). The bulletin of one manufacturer gives the pH of a 10% slurry, in water, of the ground material as 8.8 - 10.6. When such ground trihydrate is included in a dentifrice packaged in unlined aluminium tubes, one often observes swelling of the tubes or other evidence of gas formation resulting from attack on the aluminium (e.g. forming hydrogen gas) on extended storage.
The anionic phosphate esters are mixtures of mono and di-esters of the formulas hereinabove set forth. They are available from MoDo Kemi Aktiebolaget, formerly Berol Aktiebolaget, of Sweden, under the name Berol and may include an anionic tri-ester moiety too, as well as some non-ionic portion. They may be used in acid or partially or fully neutralised forms. Berol 729 has alkyl chain lengths of 16-18 carbon atoms and contains series of 4 ethylene oxide units.
Further anionic phosphate esters which may be used in acid or neutralised forms are Berol 525 which contains alkyl groups of 10-18 carbon atoms and series of 5 ethylene oxide units and Berol 513 which contains alkyl groups of 16-18 carbon atoms. Further Berol anionic phosphate esters are available as Berol 521, Berol 724 and Berol 733. The weight ratio of mono-ester to di-ester may vary, typically from about 1:10 to 10:1.
When the acid forms of the anionic phosphate ester surface active agents are neutralised or partially neutralised, alkali metal, preferably sodium, or ammonium cations are present. The surface active agent is employed in the oral preparation in amount of about 0.05-5% by weight, preferably about 0.5- 3% and most preferably about 0.5-2%. The phosphate esters serve to improve dentifrice consistency and body.
The toothpaste may comprise an additional dentally acceptable water-insoluble polishing material, such as calcined alumina, dehydrated silica, crystalline silica, having particles of sizes up to about 5 microns, a mean particle size of up to 1.1 microns and a surface area of up to 50,000 cm2 /gm, water-insoluble sodium metaphosphate (preferably substantially free of water-solubles content), tricalcium phosphate, dihydrated dicalcium phosphate, anhydrous dicalcium phosphate, calcium pyrophosphate, magnesium orthophosphate, trimagnesium phosphate, calcium carbonate, aluminium silicate, zirconium silicate, bentonite and mixtures thereof. At least 10% of the toothpaste is hydrated alumina.
The polishing material is generally present in amounts of about 20-75% by weight of a toothpaste containing it, about 30-55% being preferable. Preferably about 20-55% of the toothpaste is hydrated alumina.
In toothpaste preparations, the liquid vehicle may comprise water, typically in amount of about 10-90% by weight of the preparation. The liquid vehicle may additionally or alternatively comprise humectants such as glycerine, sorbitol solution propylene glycol. A mixture of water and glycerine and/or sorbitol solution is particularly advantageous. Preferably about 20-40% by weight of humectant and 10 to about 45% by weight of water is present.
The solid portion of the vehicle of a paste or gel composition is a gelling agent or binder such as hydroxyethyl cellulose and hydroxypropyl cellulose. These gelling agents are particularly preferred since they do not provide ions to the composition. Other gelling agents which may be used include Irish moss, gum tragacanth, sodium carboxymethyl cellulose, polyvinyl pyrrolidone, starch and water-soluble hydrophilic colloidal carboxyvinyl polymers such as those sold under the name Carbopol 934 and 940.
The toothpaste is placed in an extrudable tube of unlined aluminium for easy application to a toothbrush.
The toothpastes may include an organic surface active agent in addition to the anionic phosphate ester surface active agent. Such additional agent may be anionic, nonionic, cationic or ampholytic in nature, and it is preferred to employ as the surface-active agent a detersive material which imparts to the dentifrice detersive and foaming properties. Suitable types of such detergents are water-soluble salts of higher (i.e. having at least 12 carbon atoms) fatty acid monoglyceride monosulphates, such as the sodium salt of the monosulphated monoglyceride of hydrogenated coconut oil fatty acids, high alkyl sulphates, such as sodium lauryl sulphate, alkyl aryl sulphonates, such as sodium dodecyl benzene sulphonate, olefin sulphonates, such as sodium olefin sulphonate in which the olefin group contains 12- 21 carbon atoms, higher alkyl sulphoacetates, higher fatty acid esters of 1,2-dihydroxy propane sulphonates, and the substantially saturated higher aliphatic acyl amides of lower (i.e. having not more than 4 carbon atoms) aliphatic amino carboxylic acid compounds, such as those having 12- 16 carbons in the fatty acid, alkyl or acyl radicals. Examples of the last mentioned amides are N-lauroyl sarcosine, and the sodium, potassium and ethanolamine salts of N-lauroyl, N-myristoyl or N-palmitoyl sarcosine, which should be substantially free from soap or similar higher fatty acid material which tends to substantially reduce the effect of these compounds. The use of these sarcosine compounds in dentifrices is particularly advantageous since these materials exhibit a prolonged and marked effect in the inhibition of acid formation in the oral cavity due to carbohydrates breakdown in addition to exerting some reduction in the solubility of tooth enamel in acid solutions.
Other particularly suitable surface-active materials include nonionic agents such as condensates of sorbitan monostearate with approximately 60 moles of ethylene oxide, condensates of ethylene oxide with propylene oxide condensates of propylene glycol ("Pluronics"-PLURONIC is a Trade Mark) and amphoteric agents such as quaternised imidazole derivatives, which are availabe under the trade name "Miranol" such as Miranol C2M. Cationic surface active germicides and antibacterial compounds such as diisobutylphenoxyethoxyethyl dimethyl benzyl ammonium chloride, benzyl dimethyl stearyl ammonium chloride, tertiary amines having one fatty alkyl group (of from 12- 18 carbon atoms) and two (poly) oxyethylene groups attached to the nitrogen (typically containing a total of from 20 to 50 ethanoxy groups per molecule) and salts thereof with acids, and compounds of the structure ##STR3## wherein R is a fatty alkyl group typically containing from 12 to 18 carbon atoms, and x, y and z total 3 or higher, as well as salts thereof with mineral or organic acids, may also be used. It is preferred that the total amount of surface active agent not exceed about 5% by weight of the oral composition. At least about 0.05% of the oral composition should be composed of the anionic phosphate ester surface active agent.
In certain forms of this invention a fluorine-providing compound is present in the oral preparation. These compounds may be slightly soluble in water or may be fully water-soluble. They are characterised by their ability to release fluoride ions in water and by substantial freedom from reaction with other compounds of the oral preparation. Among these materials are inorganic fluoride salts, such as suitable alkali metal, alkaline earth metal, and heavy metal salts, for example, sodium fluoride, potassium fluoride, ammonium fluoride, a copper fluoride such as cuprous fluoride, zinc fluoride, a tin fluoride such as stannic fluoride, or stannous chlorofluoride, barium fluoride, sodium fluorosilicate, ammonium fluorosilicate, sodium fluoro-zirconate, sodium monofluorophosphate, aluminium mono- and di-fluorophosphate, and fluorinated sodium calcium pyrophosphate. Alkali metal and tin fluorides, such as sodium and stannous fluorides and particularly sodium monofluorophosphate are preferred.
The amount of the fluorine-providing compound is dependent to some extent upon the type of compound, its solubility, and the type of oral preparation, but it must be a non-toxic amount. It is considered that an amount of such compound which releases a maximum of 1% by weight, based on the weight of the preparation, is satisfactory. Any suitable minimum amount of such compound may be used, but it is preferable to employ sufficient compound to release from 0.005% to 1%, most preferably about 0.1%, by weight of fluoride ion. Typically, in the cases of alkali metal fluoride and stannous fluoride, this component is present in an amount up to 2% by weight, based on the weight of the preparation, and preferably in the range of from 0.05% to 1%. In the case of sodium monofluorophosphate the compound may be present in an amount up to 7.6% by weight, more typically 0.76%.
Antibacterial agents may also be present, typically in an amount of 0.01- 5% by weight. Typical antibacterial agents include
N1 -(4-chlorobenzyl)-N5 -(2,4-dichlorobenzyl)biguanide;
p-chlorophenyl biguanide;
4-chlorobenzhydryl biguanide;
4-chlorobenzhydrylguanylurea;
N-3-lauroxypropyl-N5 -p-chlorobenzylbiguanide;
1,6-di-p-chlorophenylbiguanidohexane; (chlorohexidine);
1,6-bis(2-ethylhexylbiguanido)hexane;
1-(lauryldimethylammonium)-8-(p-chlorobenzylidimethylammonium) octane dichloride;
5,6-dichloro-2-guanidinobenzimidazole;
N1 -p-chlorophenyl-N5 -laurylbiguanide;
5-amino-1,3-bis(2-ethylhexyl)-5-methylhexahydro pyrimidine; and their non-toxic acid addition salts.
Various other materials may be incorporated in the oral preparations of this invention. Examples are colouring or whitening agents, preservatives, silicones, chlorophyll compounds, and ammoniated material such as urea, diammonium phosphate, and mixtures thereof. These adjuvants, where present, are incorporated in the preparations in amounts which do not substantially adversely affect the properties and characteristics desired.
Any suitable flavouring or sweetening materials may also be employed. Examples of suitable flavouring constituents are flavouring oils, e.g. oils of spearmint, peppermint, wintergreen, sassafras, clove, sage, eucalyptus, marjoram, cinnamon, lemon and orange, and methylsalicylate. Suitable sweetening agents include sucrose, lactose, maltose, sorbitol, sodium cyclamate, perillartine, and saccharin. Suitably, flavour and sweetening agent may together comprise from 0.01% to 5% or more of the preparation.
The toothpaste typically has a pH of about 4 - 10, preferably about 5 - 9. When reference is made to the pH herein, it is intended that the pH determination be made directly on the toothpaste.
The toothpastes are typically prepared by dispersing polishing material in the dental vehicle and adding the phosphate ester and other components thereto.
The following specific examples are further illustrative of the nature of the present invention although it is understood that the invention is not limited thereto. All amounts are by weight unless otherwise indicated.
The following toothpastes are prepared by mixing gelling agent and sweetener with humectant, thereafter adding polishing agent, whitener, water and surface-active agent, and finally flavour. The toothpastes are deaerated and placed in unlined aluminium tubes.
______________________________________ Parts by weight ______________________________________ Glycerine 20.00 Hydroxyethyl Cellulose 1.30 Sodium Saccharine 0.20 Titanium Dioxide 0.50 Water 24.00 Alpha Alumina Trihydrate 51.50 (British Aluminium AF 260) Phosphate Ester (as indicated below) 1.50 Flavour 1.00 ______________________________________
The following phosphate esters are employed, resulting in toothpastes having the pH valves indicated:
______________________________________ Phosphate Ester Toothpaste pH ______________________________________ Berol 513 (acid form) 6.3 Berol 525 (acid form) 5.4 Berol 521 (acid form) 9.5 Berol 729 (acid form) 3.7 Berol 729 (fully neutralised) 9.1 ______________________________________
The toothpastes remain satisfactorily compatible with the unlined aluminium tubes which contain them upon storage for 6 months at room temperature, at accelerated aging conditions of 43° C. for 3 months.
Similar desirable tube compatibility occurs when the Berol phosphate esters are used in their fully neutralised or partially neutralised forms in place of the acid forms.
Likewise desirable tube compatibility occurs when the above toothpaste formulation containing the various phosphate esters includes 4.723 parts of 1,6-di-(p-chlorophenyl biguanido)hexane digluconate (20% soln) in one set of cases or 0.76 parts of sodium monofluorophosphate in another set of cases, with the formula amount of water being correspondingly reduced.
The following toothpaste is prepared, deaerated and placed in unlined aluminium tubes:
______________________________________ Parts by weight ______________________________________ Glycerine 20.202 Sodium Carboxymethyl Cellulose 1.10 Water 27.16 Sodium Saccharine 0.20 Alpha Alumina Trihydrate 52.00 (British Aluminium AF 260) Titanium Dioxide 0.5 Sodium N-Lauroyl Sarcosinate 1.538 Berol 513 (Partially neutralised form) 0.50 Flavour 0.80 Toothpaste pH 7.2 ______________________________________
The toothpaste remains compatible with the aluminium tube upon accelerated aging for 3 months at 43° C. as well as upon aging at room temperature for 3 months.
The foregoing examples are given by way of illustration and variations may be made without departing from the spirit of the invention.
Claims (7)
1. A toothpaste comprising a dentally acceptable oral vehicle and dispersed therein about 20-75% by weight of a polishing material including ground alpha-alumina trihydrate having an average particle diameter in a range of about 2 to 20 microns wherein the pH of a 10-20% by weight of a slurry of the alpha alumina trihydrate prior to grinding is in the range of about 7.5-9.5 and the pH of such a slurry after said grinding is higher than before grinding and is above 8, said alpha alumina trihydrate being present in amount of at least 10% by weight of the toothpaste, and about 0.5-3% by weight of an anionic phosphate ester surface active agent comprising a mixture of mono ester of the formula ##STR4## wherein R is an alkyl group of 10 - 20 carbon atoms, n is an integer from 1 - 6 and M is selected from the group consisting of hydrogen, alkali metal and ammonium, said toothpaste having a pH toothpaste of about 5 - 9, said anionic phosphate ester surface active agent being effective to provide consistency and body to said toothpaste and render said toothpaste compatible with an unlined aluminum container.
2. The toothpaste claimed in claim 1 wherein said anionic phosphate ester contains 16-18 carbon atoms.
3. The toothpaste claimed in claim 2 wherein R in said anionic phosphate ester contains a series of four ethylene oxide units.
4. The toothpaste claimed in claim 1 wherein said anionic phosphate ester contains 10 - 18 carbon atoms and R in said anionic phosphate ester contains a series of five ethylene oxide units.
5. The toothpaste claimed in claim 1 wherein the ratio of mono-ester to di-ester in said anionic phosphate ester varies from about 1:10 to 10:1 by weight.
6. The toothpaste claimed in claim 1 wherein said anionic phosphate ester is present in amount of about 0.5-2% by weight.
7. A packaged toothpaste wherein the toothpaste of claim 1 is in an unlined aluminium container and in contact with the aluminium surface of said container.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB179875A GB1475252A (en) | 1975-01-15 | 1975-01-15 | Toothpaste composition |
GB1798/75 | 1975-01-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
US4123517A true US4123517A (en) | 1978-10-31 |
Family
ID=9728203
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/645,743 Expired - Lifetime US4123517A (en) | 1975-01-15 | 1975-12-31 | Toothpaste compositions |
Country Status (15)
Country | Link |
---|---|
US (1) | US4123517A (en) |
AU (1) | AU507230B2 (en) |
BE (1) | BE837515A (en) |
CA (1) | CA1077398A (en) |
CH (1) | CH620360A5 (en) |
DE (1) | DE2600709C2 (en) |
DK (2) | DK14576A (en) |
ES (1) | ES444256A1 (en) |
FR (1) | FR2357242A1 (en) |
GB (1) | GB1475252A (en) |
IT (1) | IT1052936B (en) |
MX (1) | MX143070A (en) |
PH (1) | PH11907A (en) |
SE (1) | SE418054B (en) |
ZA (1) | ZA758013B (en) |
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4212856A (en) * | 1977-12-07 | 1980-07-15 | Lever Brothers Company | Toothpaste |
US4238476A (en) * | 1978-05-19 | 1980-12-09 | Colgate Palmolive Company | Dentifrices |
US4248860A (en) * | 1978-11-01 | 1981-02-03 | Lever Brothers Company | Dentifrices and their preparation |
US4264580A (en) * | 1979-04-23 | 1981-04-28 | Barberio Giacinto G | Dental cream composition |
US4301143A (en) * | 1979-12-17 | 1981-11-17 | Colgate-Palmolive Company | Dental cream composition |
US4350680A (en) * | 1980-09-24 | 1982-09-21 | Colgate-Palmolive Company | Dentifrice |
US4431630A (en) * | 1981-05-08 | 1984-02-14 | Colgate-Palmolive Company | Dentifrice composition |
US4448766A (en) * | 1982-04-29 | 1984-05-15 | Colgate-Palmolive Company | Dentifrice composition |
US4455294A (en) * | 1982-11-17 | 1984-06-19 | Colgate-Palmolive Company | Stable dentifrice containing acidic siliceous polishing agent |
US4455293A (en) * | 1981-11-19 | 1984-06-19 | Colgate-Palmolive Company | Stable dentifrice containing neutral siliceous polishing agent |
US4459283A (en) * | 1980-08-19 | 1984-07-10 | Kenneth Harvey | Stable dentifrice |
US4490353A (en) * | 1983-07-13 | 1984-12-25 | Colgate-Palmolive Company | Antiplaque dentifrice with improved fluoride stability |
US4526778A (en) * | 1981-11-19 | 1985-07-02 | Colgate-Palmolive Company | Stable dentifrice containing neutral siliceouse polishing agent |
US4528182A (en) * | 1983-07-13 | 1985-07-09 | Colgate-Palmolive Company | Stable antiplaque dentifrice with improved foaming |
US4576816A (en) * | 1979-10-27 | 1986-03-18 | Lion Corporation | Dentifrice composition |
US4581228A (en) * | 1980-11-20 | 1986-04-08 | Lion Corporation | Toothpaste composition and plastic containers containing the same |
US5019373A (en) * | 1988-12-01 | 1991-05-28 | Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. | Oral composition |
US5032383A (en) * | 1988-02-12 | 1991-07-16 | Alcan International Limited | Alumina hydrate-containing toothpaste |
US5039514A (en) * | 1988-02-12 | 1991-08-13 | Alcan International Limited | Alumina hydrate-containing toothpaste |
WO2008157197A1 (en) | 2007-06-12 | 2008-12-24 | Rhodia Inc. | Mono-, di- and polyol alkoxylate phosphate esters in oral care formulations and methods for using same |
US20100297197A1 (en) * | 2009-05-21 | 2010-11-25 | Bruce Alan Golden | Non-fluoride containing dietary supplement toothpaste and methods of using the same |
US9889089B2 (en) | 2016-04-04 | 2018-02-13 | Golden Products Llc | Dietary supplement non-fluoride toothpaste and methods of making and using same |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1599689A (en) * | 1978-05-25 | 1981-10-07 | Colgate Palmolive Co | Dental cream composition |
US4988498A (en) * | 1989-07-27 | 1991-01-29 | Unilever Patent Holdings B.V. | Oral compositions |
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US3060098A (en) * | 1957-11-18 | 1962-10-23 | Lever Brothers Ltd | Dentifrice |
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US3662060A (en) * | 1968-10-29 | 1972-05-09 | Lever Brothers Ltd | Toothpastes comprising stabilized milled alpha-alumina trihydrate |
US3670076A (en) * | 1970-03-31 | 1972-06-13 | Indiana University Foundation | Dental prophylaxis composition comprising alumina of particular particle size |
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US3957968A (en) * | 1973-08-20 | 1976-05-18 | Colgate-Palmolive Company | Dentifrices containing flat flakes of alpha-alumina |
-
1975
- 1975-01-15 GB GB179875A patent/GB1475252A/en not_active Expired
- 1975-12-29 ZA ZA758013A patent/ZA758013B/en unknown
- 1975-12-30 SE SE7514749A patent/SE418054B/en not_active IP Right Cessation
- 1975-12-31 US US05/645,743 patent/US4123517A/en not_active Expired - Lifetime
-
1976
- 1976-01-05 MX MX162844A patent/MX143070A/en unknown
- 1976-01-06 AU AU10041/76A patent/AU507230B2/en not_active Expired
- 1976-01-09 FR FR7600431A patent/FR2357242A1/en active Granted
- 1976-01-09 DE DE2600709A patent/DE2600709C2/en not_active Expired - Lifetime
- 1976-01-12 PH PH17959A patent/PH11907A/en unknown
- 1976-01-13 ES ES444256A patent/ES444256A1/en not_active Expired
- 1976-01-13 BE BE163473A patent/BE837515A/en unknown
- 1976-01-14 IT IT47630/76A patent/IT1052936B/en active
- 1976-01-14 DK DK14576*#A patent/DK14576A/en not_active Application Discontinuation
- 1976-01-14 CA CA243,514A patent/CA1077398A/en not_active Expired
- 1976-01-15 CH CH46676A patent/CH620360A5/de not_active IP Right Cessation
-
1987
- 1987-06-16 DK DK306287A patent/DK306287A/en not_active Application Discontinuation
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US3227617A (en) * | 1955-04-25 | 1966-01-04 | Colgate Palmolive Co | Fluoride dentifrice composition |
US3034967A (en) * | 1955-08-08 | 1962-05-15 | Colgate Palmolive Co | Fluoride dentifrice with insoluble alkali metal metaphosphate and aluminum compound polishing material |
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US3670076A (en) * | 1970-03-31 | 1972-06-13 | Indiana University Foundation | Dental prophylaxis composition comprising alumina of particular particle size |
US3822345A (en) * | 1971-03-19 | 1974-07-02 | Colgate Palmolive Co | Dentifrice composition |
US3937805A (en) * | 1971-11-10 | 1976-02-10 | Colgate-Palmolive Company | Method of making dentifrice compositions containing insolubilized salts of 1,6-di-(p-chlorophenyl biguanido) hexane |
US3957968A (en) * | 1973-08-20 | 1976-05-18 | Colgate-Palmolive Company | Dentifrices containing flat flakes of alpha-alumina |
Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4212856A (en) * | 1977-12-07 | 1980-07-15 | Lever Brothers Company | Toothpaste |
US4238476A (en) * | 1978-05-19 | 1980-12-09 | Colgate Palmolive Company | Dentifrices |
US4248860A (en) * | 1978-11-01 | 1981-02-03 | Lever Brothers Company | Dentifrices and their preparation |
US4264580A (en) * | 1979-04-23 | 1981-04-28 | Barberio Giacinto G | Dental cream composition |
US4576816A (en) * | 1979-10-27 | 1986-03-18 | Lion Corporation | Dentifrice composition |
US4301143A (en) * | 1979-12-17 | 1981-11-17 | Colgate-Palmolive Company | Dental cream composition |
US4459283A (en) * | 1980-08-19 | 1984-07-10 | Kenneth Harvey | Stable dentifrice |
US4350680A (en) * | 1980-09-24 | 1982-09-21 | Colgate-Palmolive Company | Dentifrice |
US4581228A (en) * | 1980-11-20 | 1986-04-08 | Lion Corporation | Toothpaste composition and plastic containers containing the same |
US4431630A (en) * | 1981-05-08 | 1984-02-14 | Colgate-Palmolive Company | Dentifrice composition |
US4526778A (en) * | 1981-11-19 | 1985-07-02 | Colgate-Palmolive Company | Stable dentifrice containing neutral siliceouse polishing agent |
US4455293A (en) * | 1981-11-19 | 1984-06-19 | Colgate-Palmolive Company | Stable dentifrice containing neutral siliceous polishing agent |
US4448766A (en) * | 1982-04-29 | 1984-05-15 | Colgate-Palmolive Company | Dentifrice composition |
US4455294A (en) * | 1982-11-17 | 1984-06-19 | Colgate-Palmolive Company | Stable dentifrice containing acidic siliceous polishing agent |
US4490353A (en) * | 1983-07-13 | 1984-12-25 | Colgate-Palmolive Company | Antiplaque dentifrice with improved fluoride stability |
US4528182A (en) * | 1983-07-13 | 1985-07-09 | Colgate-Palmolive Company | Stable antiplaque dentifrice with improved foaming |
US5032383A (en) * | 1988-02-12 | 1991-07-16 | Alcan International Limited | Alumina hydrate-containing toothpaste |
US5039514A (en) * | 1988-02-12 | 1991-08-13 | Alcan International Limited | Alumina hydrate-containing toothpaste |
US5019373A (en) * | 1988-12-01 | 1991-05-28 | Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. | Oral composition |
WO2008157197A1 (en) | 2007-06-12 | 2008-12-24 | Rhodia Inc. | Mono-, di- and polyol alkoxylate phosphate esters in oral care formulations and methods for using same |
EP2164455A4 (en) * | 2007-06-12 | 2015-08-26 | Solvay Usa Inc | Mono-, di- and polyol alkoxylate phosphate esters in oral care formulations and methods for using same |
US20100297197A1 (en) * | 2009-05-21 | 2010-11-25 | Bruce Alan Golden | Non-fluoride containing dietary supplement toothpaste and methods of using the same |
US9066889B2 (en) | 2009-05-21 | 2015-06-30 | Golden Products Llc | Non-fluoride containing dietary supplement toothpaste and methods of using the same |
US9662294B2 (en) | 2009-05-21 | 2017-05-30 | Golden Products Llc | Non-fluoride containing dietary supplement toothpaste and methods of using the same |
US9889089B2 (en) | 2016-04-04 | 2018-02-13 | Golden Products Llc | Dietary supplement non-fluoride toothpaste and methods of making and using same |
US11103447B2 (en) | 2016-04-04 | 2021-08-31 | Golden Products Llc | Dietary supplement non-fluoride toothpaste and methods of making and using the same |
Also Published As
Publication number | Publication date |
---|---|
SE418054B (en) | 1981-05-04 |
CH620360A5 (en) | 1980-11-28 |
DK306287D0 (en) | 1987-06-16 |
SE7514749L (en) | 1976-07-16 |
DK14576A (en) | 1976-07-16 |
GB1475252A (en) | 1977-06-01 |
DE2600709A1 (en) | 1976-07-22 |
ZA758013B (en) | 1977-08-31 |
FR2357242A1 (en) | 1978-02-03 |
AU1004176A (en) | 1977-07-14 |
DK306287A (en) | 1987-06-16 |
CA1077398A (en) | 1980-05-13 |
PH11907A (en) | 1978-09-08 |
IT1052936B (en) | 1981-08-31 |
FR2357242B1 (en) | 1982-02-05 |
DE2600709C2 (en) | 1990-06-21 |
MX143070A (en) | 1981-03-10 |
ES444256A1 (en) | 1977-05-01 |
BE837515A (en) | 1976-05-03 |
AU507230B2 (en) | 1980-02-07 |
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